Tailored Branched Polyolefins by Metallocene Catalysis

Kaminsky, Werner; Hoff, Matthias; Derlin, Stefanie

doi:10.1002/macp.200700053

Cited by 34 publications

(34 citation statements)

References 26 publications

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“…However, the number of catalysts that copolymerize norbornene with propene or higher 1-alkene is very limited, and their activity and/or the molecular weight of the produced polymers is not sufficient. [58][59][60][61][62][63] Ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts were found to be active not only for 1-alkene polymerization but also for norbornene polymerization. We therefore applied these catalysts for copolymerization.…”

Section: Copolymerization Of Norbornene With 1-alkenementioning

confidence: 99%

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Shiono

2011

Polym J

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This article reviews the living homopolymerization and copolymerization of propene, 1-alkene and norbornene with ansadimethysilylene(fluorenyl)(amido)dimethyltitanium, Me 2 Si(g 3 -C 13 H 8 )(g 1 -N t Bu)TiMe 2 and its derivatives, correlating the effects of cocatalysts, solvents, polymerization conditions and the substituents of the fluorenyl ligand with catalytic features, such as livingness, initiation efficiency, propagation rate, syndiospecificity and copolymerization ability. The synthesis of novel olefin block copolymers and their catalytic synthesis are also introduced using this living system. Polymer Journal (2011) 43, 331-351; doi:10.1038/pj.2011 Keywords: cycloolefin copolymer; living polymerization; norbornene; propene; single-site catalyst; syndiospecific polymerization; 1-alkene A living polymerization system, in which neither chain transfer nor deactivation occurs, affords polymers with predictable molecular weights and narrow molecular weight distributions (MWDs). Living polymerization techniques are utilized for the synthesis of terminally functionalized polymers and block copolymers. Another feature of living polymerization is its simple kinetics. Because neither chain transfer nor deactivation occurs in living polymerization, the number of polymer chains (N) is equal to the number of active centers ([C*]), and the number-average molecular weight (M n ) directly reflects the propagation rate. In living polymerization, the propagation rate can be evaluated from the M n value and the polymerization time. As chain transfer via b-elimination and/or transmetalation with trialkylaluminum as a cocatalyst is inevitable in conventional Ziegler-Natta catalytic systems; homogeneous V(acac) 3 /Et 2 AlCl (where acac is acetylacetonate or its analog) had previously been the only catalytic system that produced syndiotactic-rich living polypropylene (PP) atThe development of metallocene catalysts has enabled us to produce a variety of uniform olefin copolymers and to control the stereoregularity of poly(1-alkene)s. 3,4 The success of metallocene catalysts has stimulated research on transition metal complexes for olefin polymerization, 5-7 so-called single-site catalysts, which has also resulted in various transition metal complexes for the living polymerization of olefins. 8,9 We have also developed a living polymerization system using ansa-dimethysilylene(fluorenyl)(amido)dimethyltitanium, Me 2 Si(Z 3 -C 13 H 8 )(Z 1 -N t Bu)TiMe 2 (1), combined with a suitable cocatalyst. The catalytic system allows not only a syndiospecific living polymerization of propene and a 1-alkene but also a living homopolymerization and copolymerization of norbornene with a 1-alkene. We investigated the effect of cocatalyst, solvent and the ligand of the titanium complex on propene polymerization in terms of the livingness of the system. We also synthesized novel olefin block copolymers with the living system. This article reviews the characteristics of 1-based catalysts for tailor-made polyolefins. SYNTHESIS AND STRUCTURES OF TIT...

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Section: Copolymerization Of Norbornene With 1-alkenementioning

confidence: 99%

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Shiono

2011

Polym J

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“…He et al [2] Extremely Color-Stable Blue Light-Emitting Polymers Based on Alternating 2,7-Fluorene-co-3,9-carbazole Copolymer Y. Cao et al [3] Tailored Branched Polyolefins by Metallocene Catalysis W. Kaminsky et al [4] Functional Star-Like Polystyrenes as Organic Supports of MeDIP(2,6-iPrPh) 2 FeCl 2 Catalyst Toward EthylenePolymerization H. Cramail et al [5] Synthesis of Functionalized NMP Initiators for Click Chemistry: A Versatile Method for the Preparation of…”

Section: Synthesis Of 3-arm Star Block Copolymers By Combination Of 'mentioning

confidence: 99%

Change is the Only Constant

Staffilani¹

2007

Macro Chemistry & Physics

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“…The LG Chemical Group conducted the copolymerization of propylene, 1-hexene, and 1-octene using H 2 C(Me 2 C 5 H 2 ) 2 ZrCl 2 -methylaluminoxane. 17 Kaminsky et al 18 conducted the copolymerization of NB and 1-hexene using several metallocene catalysts. Hou et al 19 reported the copolymerization of 1-hexene and dicyclopentadiene with a cationic CpSc complex.…”

Section: Introductionmentioning

confidence: 99%

Nickel(II) complexes bearing the bis(β‐ketoamino) ligand for the copolymerization of norbornene with a higher 1‐alkene

Xing

Chen

et al. 2011

J of Applied Polymer Sci

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A novel bis(b-ketoamino)Ni(II) complex catalyst, Ni{CF 3 C(O)CHC[N(naphthyl)]CH 3 } 2 , was synthesized, and the structure was solved by a single-crystal X-ray refraction technique. The copolymerization of norbornene with higher 1-alkene was carried out in toluene with catalytic systems based on nickel(II) complexes, Ni{RC(O)CHC[N(naphthyl)]CH 3 } 2 (R¼ ¼CH 3 , CF 3 ) and B(C 6 F 5 ) 3 , and high activity was exhibited by both catalytic systems. The effects of the catalyst structure and comonomer feed content on the polymerization activity and the incorporation rates were investigated. The reactivity ratios were determined to be r 1-octene ¼ 0.009 and r norbornene ¼ 13.461 by the Kelen-Tü dõs method for the Ni{CH 3 C(O)CHC[N(naphthyl)]CH 3 } 2 /B(C 6 F 5 ) 3 system. The achieved copolymers were confirmed to be vinyl-addition copolymers through the analysis of 1 H-NMR and 13 C-NMR. The thermogravimetric analysis results showed that the copolymers exhibited good thermal stability (decomposition temperature, T dec > 400 C), and the glass-transition temperature of the copolymers were observed between 215 and 275 C. The copolymers were confirmed to be noncrystalline by wide-angle X-ray diffraction analysis and showed good solubility in common organic solvents.

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Tailored Branched Polyolefins by Metallocene Catalysis

Cited by 34 publications

References 26 publications

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Living polymerization of olefins with ansa-dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Change is the Only Constant

Nickel(II) complexes bearing the bis(β‐ketoamino) ligand for the copolymerization of norbornene with a higher 1‐alkene

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